Detergent sulphonic acid and sulphate salts of certain amphoteric detergents



United States Patent 2,781,389 Patented Feb. 12, 1957 ice DETERGENTSULPHONIC AID AND SUL- PHATE SALTS OF CERTAIN AMPHOTERIC DETERGENTS HansS. Mannheimer, New York, N. 1.

No Drawing. Application June 13, 1956, Serial No. 591,033

6 Claims. (Cl. 260458) FORMULA I Y Y R-D (IL -R2) PIG-R5- C OM in whichR is a hydrocarbon radical of at least 6 carbon atoms and for mostpurposes is 6-18 carbon atoms and may be aliphatic oraliphatic-aromatic; D is selected from the class consisting of CH andCONHRz; R2 is unsubstituted or hydroxy substituted aliphatic hydrocarbonradical of 2-4 carbon atoms, such as CzH4, CsHs, CsHsOH; Y is selectedfrom the class consisting of hydrogen, R7 and RsCOOM; R is an aliphatichydrocarbon group of 1-4 carbon atoms, such as CH2, Cal-I4, CsHs, C4Hsor an hydroxy substituted aliphatic hydrocarbon group of 2-4 carbonatoms, such as CHzCHOI-ICHz, or an aliphatic ether group of 3-4 carbonatoms containing a single ether oxygen linkage therein and otherwisebeing hydrocarbon or hydroxy substituted hydrocarbon; R is selected fromthe class consisting of CH and monovalent radicals otherwise defined asR2 such as CzHs, Cal-I7, CHzOH, C2II4OH, etc.; a is an integer in therange of 1-5; M is an alkali metal and preferably sodium or potassium.

Said polyamino acid metal salts may be produced in a number of differentways well known to the art. For example, RCOOH may be reacted with apolyamine NH2R2(NHRZ)$NH2 in the mole proportion of 1 to l and water ofreaction is removed in the well known manner to provide:

RCONHR2(NHR2)NH2 For example, a hydrocarbon chloride RCHzCl is reactedwith a polyamine NH2R2NH2 in the mole proportion of 1 to l andthehydrochloride of reaction is removed with caustic soda to produce:

For example a hydrocarbon chloride RCHzCl may be reacted with H(NHR2)NH2in the mole proportion of l to 1 and the hydrochloride of reaction isremoved with caustic soda to provide:

RCHz (NI-1R2 2NH2 Compounds of the last formula may be produced byreacting RNH with ethylene oxide and ammonia.

Many polyamines are readily available in large commercial quantities.These amines are preferably employed in the production of my startingmaterials of this invention and have the following formulas andhereinafter known as reactants A, B, C, and D respectively:

These particular polyamines are generally produced by reacting ethyleneoxide with ammonia. Polyamines containing additional ethyl amino groupscan be obtained in the same manner. By employing propylene oxide insteadof ethylene oxide homologues of the polyamines above set forth may beobtained, which contain propyl groups instead of the ethyl groupstherein.

For example, glycerol polyamines may be prepared by reacting 1 mole ofepichlorhydrin is reacted with 2 moles of aqueous ammonia in the wellknown manner to produce NHzCI-IzCI-IOHCI-IzNHzI-ICI which is treatedwith caustic soda to remove the HCl to provide reactant E.

NHzCHzCHOHCI-IzNHz which may be reacted with RCH2C1 in equirnolecularproportions to provide compounds:

which may be employed in the production of starting materials.

Said NHzCHzCHOHCHzNHz may be reacted with NHZCHZCHOHCHZCI in the moleproportion of 1 to 1 and subsequently treated with caustic soda toremove the HCl to provide reactant F.

Said NHzCHzCHOHCHzNHz may be reacted epichlorhydrin in the mole ratio of2 to l and subsequently treated with caustic soda to obtain reactant G.

NHQCHzCHOHCI-IzNHCHzCHOHCHz NHCHzCHOHCHzNHz For example, butylpolyamines may be obtained by reacting butyl diamine NH'zCrI-IaNHz withbutyl dichloride in the mole proportion of 2-1 and in the presence. ofcaustic soda to obtain reactant H.

NHzCtHsNHCrI-IeNI-ICeHsNHz For example 1 mole of said polyaminesexamples of which are reactants A-H may be respectively reacted with 1mole respectively of lauryl bromide C11H23.-CH 2--Br, capric bromide,C9l-li9CI-I2-Br, nonyl benzyl chloride C9H19CsH4CHzCl and subsequentlytreated with caustic soda to remove the HCl or HBr formed in the courseof reaction to produce compounds in which a hydrogen of only one-of theterminal NH groups is replaced by C11H23-CH2-, C9H19-C Hz,CsH19CsH4--CH2-- with such methods being known to the art.

For example, 1 mole respectively of reactants B-E, G-H may be reactedwith 1 mole of lauricacid C11H23COOH capric acid CQHIQCQOH, nonylbenzoic acid C9H19-C6H4.COOH

until 1 mole of water of reaction has been formed and removed to providecompounds in which C11H2sCO-, CH19-CO-, and CsH19CsH4CO- respectivelyare substituted for a single hydrogen of only one of the terminal NHzgroups, such methods being well known to the art.

The starting materials of this invention may be produced by reacting apolyamine which is at least a diamine with R-CHshalogen and subsequentlytreated with caustic soda, or a polyamine which is at least a triaminewith RCOOH to provide Y R-D-(dI-Rr) n NHB which may be reacted withmonohalocarboxylic acid together with caustic soda or potassiumhydroxide. The monohalocarboxylic acid generally used may bemonochloracetic, monochlorlactic, monochlorpropionic, etc. so that R isCH2, C2H4, CsHa, C4Hs, CHzCHOI-l, etc. In general the reaction iscarriedout by employing 1 mole of said compound and 1 or more moles ofmonohalocar- .boxylic acid and 2 moles of caustic soda or potassiumhydroxide for each mole of monohalocarboxylic acid used. If the numberof moles of monohalocarboxylic acid employed is less the number ofhydrogens on the amine groups, apart from the H of the CONH group ifsaid group is present, then 1 or more of them if desired may be reactedwith CHaCl, C2H5Cl, CsH'zCl, ethylene chlorhydrin etc. then with causticto provide radicals such as CaHs, Cal-I7, C2H4OH etc. for one or more ofsuch hydrogens.

The following are given merely by way of illustrating in general methodswell known to the art for producing examples of starting materials whichmay be employed in the practice of this invention.

Examples A-H 1 mole of C11H2sCH2NHC2H4NH2 is reacted with 1 mole ofmonochloracetic acid together with 2 moles of caustic soda to provideproduct A:

1 mole of product A is reacted with 1 mole of monochlorlactic acidtogether with 2 moles of caustic soda to provide a mixture of product Band product B-l of the following formulas:

H nHzs- H2 OZHAN/ CHr-O O 0 N8.

H CHnCHOEL-COONa and OHSCHOH-OO ONa OuHts-CHz-NHCzHt-N CHz- C O O Na 1mole of mixture of products B and B-1' is reacted with 1 mole ofmonochlorpropionic acid together with 2 moles of caustic soda to provideproducts C and 0-1 which are the same as products B and B-1 respectivelyexcept that C2H4COONa is substituted for the hydrogens thereof attacheddirectly to the nitrogens.

' 1 mole of product A is reacted with 2 moles respectively of methylchloride and subsequently treated with caustic soda to remove the HCl ofreaction to provide product D:

1 mole of product A is reacted with 2 moles of ethylene chlorhydrin and2 moles of caustic soda to provide product E:

CsHaOH C11 :a CH2-N CaH4N O2H4OH CHz-OOONu 1 mole of product A isreacted with 2 moles of monochloracetic acid together with 4 moles ofcaustic soda to provide product F.

CHr-C O 0N3 CuHtr-CHr-N CaH4N CHPOOONB:

CHE-CO 0N5 Using the same type of reactants as those employed for theproduction of product A except that are respectively substituted for theradical C11H23CH2 to provide products G and H which are the same asproduct F, except that said two radicals are respectively substitutedfor the C11H23-CH2 of product F.

Examples I-CC 1 mole of C11H23CHzNHC2H4(NHC2H4)sNHz is reacted with 1mole of monochloracetic acid together with 2 moles of caustic soda toreplace a hydrogen of the NHz with CH2COONa to provide product I.

1 mole of product I is reacted with 1-5 moles respectively ofmonochloracetic acid and 2-10 moles of caustic soda respectively toreplace 1-5 of the hydrogen atoms attached directly to the nitrogenatoms thereof with 1-5 of -CHzCOONa to provide products J-N.

1 mole of product I is reacted with 1-5 moles respectively of ethylenechlorhydrin and caustic soda to replace 1-5 of the atoms attacheddirectly to the nitrogen atoms thereof with 1-5 of -C2H4OH to provideproducts 0-8.

1 mole of product I is reacted with 1-4 moles respectively of ethylenechlorhydrin and caustic soda to replace 1-4 of the hydrogens attacheddirectly to the nitrogen atoms with -CzH4OI-l to provide products T-W.

1 mole of product K is reacted with 1-3 moles respectively of ethylenechlorhydrin and caustic soda to replace l-3 of the hydrogen atomsattached directly to the nitrogen atoms with -C2H4OH to provide productsX-Z.

1 mole of product L is reacted with l-2 moles respectively of ethylenechlorhydrin and caustic soda to replace 1-2 of the hydrogen atomsattached directly to the nitrogen atoms with C2H4OH to provide productsAA and BB.

1 mole of product M is reacted with 1 mole of ethylene chlorhydrin andcaustic soda to replace the single hydrogen connected directly to anitrogen atom with -C2H4OH to provide product CC.

Examples DD-Il 1 mole of C11H23-CONH-C2H4NHC2H4NH2 is reacted with 1mole of monochloracetic acid together with 2 moles of caustic soda toprovide product DD:

1 mole of product DD is reacted with l-2 moles respectively ofmonochloracetic acid and 2-4 moles of caustic soda respectively toprovide respective products EE and FF having the following respectiveformulas:

H C1 Hz3 C O NH- UZHJN czH N CHa-C O O Na CHa C O O N a and CH2- C O O N5 CuHgs- C O NH C2H4N CsH4N CHa-C O O Na CHr- C O O Na 1 mole of productDD is reacted with l-Z moles respectively of ethylene chlorhydrin andcaustic soda to provide products GG and res ectiv lyhaving the followingrespective formulas:

zHiOH CHB-COON hydrin and then treated with 6 moles of caustic soda, andwhereby two CHzCOONa groups and twov C2 Hi0I-l OH OH groups replace thehydrogens attached to the nitrogen groups other than that in theCONHCzI-Is groups The CiiHis- ONHCzH4NC2Hi product is W.

,H4OH CHPCOOM. The specific nionocarboxylic acids, as well as the spe- 1mole of product HH is reacted with 2 moles of cifiemonohalomonoearboxylic acids employed in certain monochloracetic acidand 2 moles of monochlorlactic am k may be la by 9 as may be i acidrespectively together with 4 moles of caustic soda varother the sPeclfici k 9 Prelude respectively to provide products HH and II of the folagreat number of qther Starting matnalst which dlfier lowing respectiveformulas: from those set forth in the examples heretofore setforth.

Prior to T1118 invention, it was known that cationic sur- CHQCHPCOOMface active agents and anionic surface active agents whenCiiHiii-C0NH-C2H4NC2H4N together in aqueous solution resulted in theproduction CHPCOOM or formation of water insoluble compounds, and thatadding an anionic surface active agent to an aqueous solu- CQHOCHPCOONEtion of another anionic surface active agent resulted in and a merephysical combination of said agents and that no CH*CHiCHOHCOONa reactionwould occur between them. c,,in8-ooNH oiH4NoHiN Said polyamino acidmetal salts normally behave CHPCOONa anionically in aqueous solutionshaving a pH above 7, and consequently it was expected that saidpolyamino CZHO CHzCHOH-OOON acid metal salts when in aqueous solutiontogether with Examples J] KK agionicnsurfaize aggnttil tthat thiy wouldbet combinig p ysica y on y an a no c emicareacion wou 32:3 ::igf fgzgfi ggg? fifg :2; occur therebetween. In the course of myexperimentafeactant E 8 1 1(1 using iaustic soda, is reacted with l andi hillve discovered ihlat Saidt acid metal 3 moles respectively ofmonochlorpropionic acid together sa ts cou d be reacted with certainanionic surface act ve with 2 and 6 moles of caustic soda respectivelyto pro agents at 3 PH above to produce-wat-elpsoluble reacnon r 30products. Not only did I make said discovery, but I forproducts H andIXK respectlvely' thei discovered that water solutions of such reactionproduts had viscosities greater than corresponding aque-CQHXPCQHPCHFNHQECHOHCHZN ous solutions of polyamino acid metal salts andalso CQHPCOONa exhibited better foaming characteristics than did said 40polyamino acid metal salts in very low dilutions under and extreme waterhardness conditions. Said reaction prod- O2H4-COON$ ucts are non-toxicand non-irritating to the human skin. CQILFCSHPCHPNCHBOHOHCHN They havebeen found eminently useful as general utility Y detergents, such as forcar washing, dish washing, clothes ZHi-fCOOLQ Gilli-C washing, et-c.Said polyamino acid metal salts" as Well Examples L as compounds ofFormula II, hereinafter described and 1 mole of cnnzasoNncziiiiNi-iczniQuin is re- Physical mixtures Said Y F acid metal (NHCHzCHOCHzhNI-Iz,produced by reacting 1 mole salts and compounds of H t 9 of H w 1 mole freactant G is ponents-of shampoos sometimes caused sl ght irritationreacted with 1 mole of monochloracetic acid together Slmgmg 0f the ywhen $11611 S P were used with 2 moles of potassium hydroxide to provideprodand water solutions thereof accidentally reached the eyes. not LL: Ihave further discovered that the reaction products of /HC5H11-C6H4-CONHCHICHOHCH2(NI'ICH2CHOHCH2)IN CHa-COOK 60 this inventioncaused practically no irritation or stinging Examples MM VV of the eyeswhen so employed.

1 mole of C11H23CONHC2H4 NHC2HQ3NH2 is According to this invention, oneor a combination of acted with 1 mole of monochloracetic acid togetherwith two or W of said Polyammo meta.l salts of the 2 moles of causticsoda, whereby a hydrogen of the NI-Iz 9 l qi i Formula I F feasted 'f' agroup is replaced by CHzCOON'a which is product. MM. p f a two or moreanion-1c Surface acnve aggms 1 mole of product MM is reacted with 14moles f h followmg gn structural Formula II to P respectively ofnionochloracetic acid together with 2-8 vlde novel i lb u haimg l w gmoles of caustic soda to provide products NN, 0O, l e m m and hallmghlgh wetting PP, and QQ which are compounds the same as MM, d 'hg urfacem propemes. and capable except that l4 of the hydrogens attached to thenitrogens i f m volilmmous and w d M ss. 501m other than that of theCONHCZHQ group are replaced 99 which afiluemls Sohmons are substannanyP93 by cH2CO0Na irritating to the skin and eyes of normal human beings.

1 mole of product MM is reacted with 1--4 moles respectively of ethylenechiorhydrin and then treated with FORMULA H caustic soda, whereby 1-4 ofthe hydrogens thereof con R3'Z(C2H4O)SO3 -M 6 nected to such nitrogensother than that in the CONHCzH4 group is replaced by C2H4O'H to provideproducts RR, SS, TT, and UU.

1 mole of product MM is reacted with a mixture of 2 moles of'monochloracetic acid and 2 moles of chloravsnase FORMULA m H m-zornmrsoi b wherein R3 is a hydrocarbon radical, generally aliphatic oraliphatic-aromatic, and having at least 6 carbon atoms and for mostpurposes 6-20 carbon atoms; Z is either oxygen orsulphur; and x is aninteger and being at least 1 and generally 1-5, and preferably 3; M, R,D, R2, Rs Y, and a have heretofore been defined in Formula I; and b iszero to 5 and no greater than a; c is zero to 1; the sum of b and c isat least 1.

According to this invention, I react a compound of Formula I with acompound'of Formula II to provide the novel and highly useful compoundsof Formula III In general, this-reaction is carried out in a solutioncontaining Compounds I and II and to which a quantity of an acidic agentsuch a a strong mineral acid, as for example hydrochloric, sulphuricor'its equivalent, has been added to lower the pH of the solution to avalue of approximately 7 to approximately 9 and while maintaining themass at a temperature between approximately 100-200 F. In this reactionunder the'aforesaid conditions, the compounds of Formula IH areproduced, said compounds having high water solubility in spite of thefact that the number of carbon atoms in R3 is 6 or more. Such compoundsof Formula III have an unexpected extremely high water-solubility, whilethe corresponding salts of cationic compounds are water-insoluble. Theresultant aqueous solution can be used directly as a surface activeagent, wetting agent or detergent for the purposes indicated for thepolyamino acid metal salts. While the quantities of the compound ofFormula I and com- 3 solve about I mole of a compound of Formula I in ar quantity of water measuring about 1.5 times the weight of compound ofFormula I used and then the pH thereof is adjusted to approximately12-13 (measured electrically) by the addition of aqueous caustic soda ifrequired so that when a compound of Formula II is added thereto, the pHof the solution of I and II will be at least and generally 10.5-11. Thetemperature of said solution is raised to 100-200 F. and preferably infactory practice to approximately 140 F. Then about 1-5 moles of acompound of Formula II is dissolved in a quantity of water measuring byweight 1.5 times the quantity of compound of Formula II in .a separatecontainer and this solution is added to said first solution and the massis maintained in said temperature range while beng constantly stirred,and an acidic agent is added thereto to reduce the pH thereof to a valuebe: low 10 and in the range of approximately 7 to 9, and preferably ofapproximately 8.2 to approximately 8.7. At the end of the acidic agentaddition, the stirring is continued and the temperature of the massmaintained for about 10-20 minutes after which the solution is allowedto cool and is a finished product. i

The following are specific examples merely given by way of illustratingtheinvention and are not to be taken 8 by way of limitation, all partsbeing given by weight unless otherwise specified.

Example I An aqueous solution of 310 parts of product A in 460 parts ofwater is heated to approximately F. and its pH (measured electrically)is adjusted by the addition of aqueous caustic soda to 12-13. Whilebeing constantly stirred and maintained at that temperature, there isadded a solution of 400 parts of sodium salt of lauryldiethoxyethersulfate:

in 600 parts of water. Then while stirring and the temperature ismaintained, there is added thereto. between about 30-40 parts ofhydrochloric acid solution (32%), whereby the pH of the mass is loweredto a value in the range of 8.2 to 8.7. Stirring is continued and thetemperature maintained for about 10 minutes more. The resultant productis a solution of the novel reaction product, having the followingformula:

' H C1 Hz3-CH3-NH CEH4NCHZCO CNS Employ the same procedure andcomponents as set forth in Example 1, except that only 200 parts ofsodium salt of lauryldicthoxyether sulfate:

in 300 parts of water are used. In this instance the resultant productis a solution of the novel reaction product whose structural formula isshown in Example 1 together with unreacted product A used, in theapproximate proportion of 2 parts of the former to 1 of the latter.

Also if desired, using the same procedure and components of Example 1,except that 2 moles of compound of Formula I, such as 620 parts ofproduct A in 800 parts of'water and l-3 moles of compound ofFormula H,such as 400-1200 parts of sodium salt of lauryldiethoxyether sulphate in600-1800 parts of water to provide novel reaction product of Example Awith excess of either product A or the sulfate salt.

Employ the same procedure as that set forth in Example 1, but employ thecomponents indicated in the following examples; the quantity ofhydrochloric acid solution (32%) is variable to lower the pH to valuesindicated in Example 1 to obtain the novel reaction products of thefollowing examples.

Example 2 500 parts of product B in 750 parts of water. 500 parts ofoctylmonoethoxyether sodium salt:

in 750 parts of water.

0111-0 0 O Na Example 3 510 parts of product C in 760 parts of water.500 parts of tridecyl tetraethoxyether sulfate sodium salt:

1o FORMULA or NOVEL REACTION PRODUC Example 8 H 2765 parts of product in500 parts of water. 400 parts of decyltriethoxy thioether sulfate sodiumsalt: C1oHz1--S-'(C2H4O)3'S03--Na in 600 parts of water.

' I CHPOOONa FORMULA on NOVEL REACTION PRODUCT O1aHa7O(C2H4O)4-SO: H

Example 4 CnHta--CONH-C:HNHC:H4N

. H OH -00 ONa 450 parts of product H in 700 parts of water. 1000 partsof nonylphenoltriethoxyether sulfate sodium salt: 4 )a 0:

CH CH 0 (CH0) so Exampleg 675 parts of product II in 1,000 parts ofwater. 1,000 in 1500 parts of water. parts of amylphenylpentaethoxyethersulfate sodium salt: CsHn--CsH4O-(C2H-4O)5SO3Na in 1,500 parts FORMULAOF NOVEL REACTION PRODUCT V of water.

CHz-COONa FORMULA OF NOVEL REACTION PRODUCT CHz-COONn UCsHnCnHi-O-(C2H4O)5S0a Colin Cally-CHr-N-CzHs-N 5HttCOH4-O( CeHrO ):.-S03 H H Cnz ooom n ozrnoonzonon-coom l a arctnio czuio)a-sos n2sCONH-CzH4NC H4N CQHL'I"CGII4O (C2H4O)G SO2 H CH5 COON3C2H4OCH2CHOH-OOON3 Example 5 Example 10 425 parts or" product I in 650parts of Water. 1000 490 parts of product LL in 750 parts of Water.1,500 arts of hex lmonoethoxyether sulfate sodium salt: parts oftridecyltetraethoxy thioether sulfate potassium p J 50 1t CH s (CH0) soK 2300 t r V sa:132w---24 3 in arso COH1a-O- (C2H4O SO3-Na Water p in1509 parts Of W816i. FORMULA OF NOVEL REACTION PRODUCT l WC5Hn-CaH4-CONHCH2CHOHCH2 NHCH2CHOHCH2]N\ Lginnes-(ormmhsoa 2 OHz-COOKUiaH21-s-(C2H4O)4-S0s FORMULA OF NOVEL REACTION PRODUCT Employing thesame procedure as that set forth in H Example 1, except that 1 moleproportion of products v B-VV are respectively substituted for product Ato pro- OIHTFWNH CZH-N H vide other novel reaction products which arerespectiveiy CHPCOONQ the same as the formula of the novel reactionproduct CBHIS O (C,H4O) SOH of Example A except that there issubstituted formulas t of BL-L respectively for the formula of product Acn aoo2m0)s0i therein. I

Follow-mg the same procedure as that set forth in Example 6 Example 1and employing 1 mol of any of said other 850 parts of product N in 1300parts of Waten 600 starting materials of Formula I respectively, and 1mol parts of stearoylpentethoxy thioether sulfate sodium salt: of any ofthe other SPeclfiC COmPOHPdS of Formula in parts of waten a great numberof other novel reaction products whose formulas are that of Formula IIImay be produced; and FORMULA OF NOVEL REACTION PRODUCT in addition, thespecific reactants employed may differ C17II3iS(C2H4O)5 SO3 CH2-COONEfrom those employed herein, with-in the definitions there- '41() partsof product GG in 620 parts of water. 350 to approximately For examp Eand K may be solved together and this solution may, by the addition f ig izig g g i s gfg f g gg g' fi of caustic soda when required, have itspH adjusted to B 6 2 2 P at least 10, and then at 100400" F. is readyfor the of Water addition of the acidic agent to lower its pH toapproxi- FORMULA OF NOVEL REACTION PRODUCT mately 7 to approximately 9.If desired, the required OiHtOE H amount of acidic agent may be addedeither before or C11H23 CONH C2H4NO2H4 N/ after the solution of pH of atleast 10 is brought to a temperature in the range of IUD-200 F.

Since certain changes in carrying out the aforesaid processes andcertain modifications in the compositions CHHQWCHWNQHNCZHNCZENCZHN of,to provide a great number of other compounds of Formula III.

H CHPCOON It is to be understood that instead of first adjustingCHz-COON'A the pH of the compound of Formula I to 12-13 before i ICHPCOONQ V 60 the addition of the compound of Formula II, any other i 1method may be employed to obtain the condition wherei CLPCOON by the pHof the solution of I and II is at least 10 and CH2OOONa preferably10.5-1'1 before the addition of the acidic Example 7 agent to lower thepH of the mass to approximately 7 which embody the invention may be madewithout departing from its scope, it is intended that all mattercontained in the description shall be interpreted as illustrative andnot in a limiting sense.

It is also to be understood that the following claims are intended to.cover all the generic andspecific features of the invention hereindescribed, and all statements of [R3-Z(C2H40)r-SO3 c in which R isselected from the class consisting of aliphatic and aliphatic-aromatichydrocarbon radicals of 6-18 carbon atoms; D is selected from the classconsisting of CH2 and CONHRz; R2 is selected from the class consistingof (a) aliphatic hydrocarbon radicals of 2-4 carbon atoms, (b) hydroxysubstituted hydrocarbon radicals of 2-4 carbon atoms; Y is selected fromthe class consisting of hydrogen, (d) R7 and (e) RCOOM; R5 is selectedfrom the class consisting of (f) hydrocarbon groups of 1-4 carbon atoms,(g) hydroxy substituted hydrocarbon groups of 2-4 carbon atoms, (11)ether groups, each of said groups being of 3-4 carbon atoms, having asingle ether oxygen linkage therein and otherwise being hydrocarbon, (i)ether groups, each of said groups being of 3-4 carbon atoms, having asingle ether linkage therein and otherwise being hydroxy substitutedhydrocarbon; R1 is selected from the group consisting of CH: andmonovalent radicals otherwise defined in R2; a is 1-5; b is zero to 5and no greater than a; c is zero to l; the sum of b and c is at least 1;R3 is selected from the group consisting of aliphatic andaliphaticaromatic hydrocarbon radicals of 6-20 carbon atoms; Z isselected from the group consisting of sulphur and oxygen; x is 1-5; andM is an alkali metal.

2. A compound defined in claim 1, and with R, D, R2, R3, R4 and R5 beinghydrocarbon as therein defined, each Y being hydrogen and Z beingsulfur.

3. A compound defined in claim 1, and with D being CONHRz and R, R2, R3,R4 and R5 being hydrocarbon as therein defined, each Y being hydrogenand Z being sulfur.

4. A compound defined in claim 1, and with R, D, M, R3, R4 and R5 beinghydrocarbon as therein defined, each Y being hydrogen and Z beingoxygen.

5. A compound defined in claim 1 and with D being CONHRa and R, R2, R3,R4 and R5 being hydrocarbon as therein defined and each Y being hydrogenand Z being oxygen.

6. A compound defined in claim 1, and with R, D, R2, R3, R4 and R5 beinghydrocarbon as being therein defined and each Y being RsCOOM as thereindefined and Z being oxygen.

References Cited in the file of this patent UNITED STATES PATENTS2,097,640 Piggott Nov. 2, 1937 FOREIGN PATENTS 208,288 Switzerland Apr.16, 1940

1. A COMPOUND OF THE FOLLOWING FORMULA: